Gene therapy by virus-like self-spooling toroidal DNA condensates for revascularization of hindlimb ischemia.

Peripheral arterial diseases (PAD) have been reported to be the leading cause for limb amputations, and the current therapeutic strategies including antiplatelet medication or intervene surgery are reported to not clinically benefit the patients with high-grade PAD. To this respect, revascularization based on angiogenetic vascular endothelial growth factor (VEGF) gene therapy was attempted for the potential treatment of critical PAD. Aiming for transcellular delivery of VEGF-encoding plasmid DNA (pDNA), we proposed to elaborate intriguing virus-like DNA condensates, wherein the supercoiled rigid micrometer-scaled plasmid DNA (pDNA) could be regulated in an orderly fashion into well-defined nano-toroids by following a self-spooling process with the aid of cationic block copolymer poly(ethylene glycol)-polylysine at an extraordinary ionic strength (NaCl: 600 mM). Moreover, reversible disulfide crosslinking was proposed between the polylysine segments with the aim of stabilizing these intriguing toroidal condensates. Pertaining to the critical hindlimb ischemia, our proposed toroidal VEGF-encoding pDNA condensates demonstrated high levels of VEGF expression at the dosage sites, which consequently contributed to the neo-vasculature (the particularly abundant formation of micro-vessels in the injected hindlimb), preventing the hindlimb ischemia from causing necrosis at the extremities. Moreover, excellent safety profiles have been demonstrated by our proposed toroidal condensates, as opposed to the apparent immunogenicity of the naked pDNA. Hence, our proposed virus-like DNA condensates herald potentials as gene therapy platform in persistent expressions of the therapeutic proteins, and might consequently be highlighted in the management of a variety of intractable diseases.

Transgenerational effects of extracts containing Microcystin-LR exposure on reproductive toxicity and offspring growth inhibition in a model organism zebrafish.

Cyanobacteria cell lysates release numerous toxic substances (e.g., cyanotoxins) into the water, posing a serious threat to human health and aquatic ecosystems. Microcystins (MCs) are among the most abundant cyanotoxins in the cell lysates, with microcystin-LR (MC-LR) being one of the most common and highly toxic congeners. In this study, zebrafish (Danio rerio) were exposed to different levels MC-LR that from extracts of Microcystis aeruginosa. Changes in the MC-LR accumulations, organ coefficients, and antioxidant enzyme activities in the zebrafish were analyzed. Transgenerational reproductive toxicity of MC-LR in the maternal and paternal generations was further investigated, as well as the influences of extracts containing MC-LR exposures of the F1 on the growth of zebrafish. The study found that high levels of MC-LR could be detected in the major organs of adult zebrafish, particularly in spleen. Notably, concentration of MC-LR in the spermary was significantly higher than that in the ovarium. MC-LR could induce oxidative damage by affecting the activities of catalase and superoxide dismutase. Inherited from F0, MC-LR led to impaired development in the F1 generation. Difference in offspring survival rates could be observed in the groups with different MC-LR levels of maternal and paternal exposures. This study reveals transgenerational effects of MC-LR on the reproductive toxicity and offspring growth inhibition to the aquatic organisms, which should be emphasized in the future ecological risk assessment.

Alkylphenols disrupt estrogen homeostasis via diradical cross-coupling reactions: A novel pathway of endocrine disruption.

Estrogen, being an essential class of sex hormone, is an important target of endocrine disruption chemicals. It is well known that environmental disruptors could activate or inhibit estrogen receptors, acting as agonists or antagonists, and thus affect the circulating estrogen concentrations. Here, we report enzyme-mediated diradical cross-coupling reactions between alkylphenols (e.g., 2,4-di-tert-butylphenol [DBP], 4-nonylphenol [4-NP], and 4-tert-octylphenol [4-t-OP]) and estrogens (e.g., estradiol [E2]) that generate coupling metabolites and disrupt estrogen homeostasis. Among the phenolic xenobiotics, the screening of metabolic products revealed that alkylphenols had the highest reaction activities and generated coupling metabolites with high abundances (DBP-O-E2, 4-t-OP-O-E2, and 4-NP-O-E2). The coupling reactions were catalyzed by cytochrome P450 3A4 (CYP3A4) and verified by the detection of the coupling products in general populations. In vitro and in vivo exposures together with CYP3A4 inhibition demonstrated that cross-coupling reactions of phenols and E2 significantly reduced the normal levels of E2. We further established a unique spin-trapping-based high-throughput screening method to show the existence of diradicals in the coupling reaction. Density functional theory calculations revealed that spin aromatic delocalization was the fundamental cause of the high rebound barrier and sufficient lifetime of phenoxy radicals that enabled phenolic cross-coupling triggered by cytochrome P450. The identified mechanistic details for diradical cross-coupling reactions provide a novel pathway for phenolic chemicals to disrupt estrogen homeostasis.

Insight into the dynamics of dissolved organic matter components under latitude change perturbation.

Dissolved organic matter (DOM) which can help the transportation of nutrients and pollutants plays essential role in the aquatic ecosystems. However, the dynamics of individual DOM component under the change of latitude have not been elucidated to date. The composition and dynamics of DOM were assessed in this study. Two individual parallel factor analysis (PARAFAC) components were found in each sampling site in Heilongjiang. To further characterize the inner change of the identified PARAFAC components, two-latitude correlation spectroscopy (2DCOS) technique was applied to the excitation loadings data. Interestingly, not all the fluorophore in a PARAFAC component change in the same direction as the overall change of a component. From upstream to downstream, the peak A1 in PARAFAC component C1 showed a downward trend, but peak A2 presented an upward trend. In PARAFAC component C2, the peak T2 and peak T3 showed an inverse changing trend under latitude perturbation. Furthermore, basic nutrients parameters in Heilongjiang were also characterized in each sampling sites. The relationships between DOM and nutrients showed that component C1 made a significant contribution to chemical oxygen demand (COD) and biochemical oxygen demand (BOD5). The evolutions of DOM peak A1 and peak A2 were accompanied by the changing of Total phosphorus (TP). The findings in this study could make a contribution to explore the fate of DOM in high humic-like substance containing river.

Spatially Resolved Co-Imaging of Polyhalogenated Xenobiotics and Endogenous Metabolites Reveals Xenobiotic-Induced Metabolic Alterations.

A large group of polyhalogenated compounds has been added to the list of persistent organic pollutants in a global convention endorsed by over 100 nations. Once entering the biotas, these pollutants are transported to focal sites of toxicological action and affected endogenous metabolites, which exhibited distinct tissue or organ distribution patterns. However, no study is available to achieve simultaneous mapping of the spatial distributions of xenobiotics and endogenous metabolites for clarifying the molecular mechanism of toxicities. Herein, we present a sensitive mass spectrometry imaging method─tetraphenyl phosphonium chloride-enhanced ionization coupled with air flow-assisted ionization-Orbitrap mass spectrometry─which simultaneously determined the spatial distributions of polyhalogenated xenobiotics and endogenous metabolites. The spatially resolved toxicokinetics and toxicodynamics of typical polyhalogenated compounds (chlorinated paraffins (CPs) and hexabromocyclododecane (HBCD)) were assessed in zebrafish. Co-imaging of polyhalogenated compounds and metabolites visualized the major accumulation organs and maternal transfer of HBCD and CPs, and it clarified the reproductive toxicity of HBCD. CPs were accumulated in the liver, heart, and brain and decreased the concentrations of polyamine/inosine-related metabolites and lipid molecules in these organs. HBCD accumulated in the ovary and was effectively transferred to eggs, and it also disrupted normal follicular development and impaired the production of mature eggs from the ovary by inhibiting expressions of the luteinizing hormone/choriogonadotropin receptor gene. The toxic effects of metabolic disruptions were validated by organ-specific histopathological examinations. These results highlight the necessity to assess the distributions and bioeffects of pollutants in a spatial perspective.

Enzyme-Catalyzed Hydrogen-Deuterium Exchange between Environmental Pollutants and Enzyme-Regulated Endogenous Metabolites.

Environmental pollutants can disrupt the homeostasis of endogenous metabolites in organisms, leading to metabolic disorders and syndromes. However, it remains highly challenging to efficiently screen for critical biological molecules affected by environmental pollutants. Herein, we found that enzyme could catalyze hydrogen-deuterium (H-D) exchange between a deuterium-labeled environmental pollutant [D38-bis(2-ethylhexyl) phthalate (D38-DEHP)] and several groups of enzyme-regulated metabolites [cardiolipins (CLs), monolysocardiolipins (MLCLs), phospholipids (PLs), and lysophospholipids (LPLs)]. A high-throughput scanning identified the D-labeled endogenous metabolites in a simple enzyme [phospholipase A2 (PLA2)], enzyme mixtures (liver microsomes), and living organisms (zebrafish embryos) exposed to D38-DEHP. Mass fragmentation and structural analyses showed that similar positions were D-labeled in the CLs, MLCLs, PLs, and LPLs, and this labeling was not attributable to natural metabolic transformations of D38-DEHP or incorporation of its D-labeled side chains. Molecular docking and competitive binding analyses revealed that DEHP competed with D-labeled lipids for binding to the active site of PLA2, and this process mediated H-D exchange. Moreover, competitive binding of DEHP against biotransformation enzymes could interfere with catabolic or anabolic lipid metabolism and thereby affect the concentrations of endogenous metabolites. Our findings provide a tool for discovering more molecular targets that complement the known toxic endpoints of metabolic disruptors.

Molecular docking and in vitro evaluations reveal the role of human cytochrome P450 3A4 in the cross-coupling metabolism of phenolic xenobiotics.

Metabolism generally transforms xenobiotics into more polar and hydrophilic products, facilitating their elimination from the body. Recently, a new metabolic pathway that transforms phenolic xenobiotics into more lipophilic and bioactive dimer products was discovered. To elucidate the role of cytochrome P450 (CYP) enzymes in mediating this cross-coupling metabolism, we used high-throughput screening to identify the metabolites generated from the coupling of 20 xenobiotics with four endogenous metabolites in liver microsomes. Endogenous vitamin E (VE) was the most reactive metabolite, as VE reacted with seven phenolic xenobiotics containing various structures (e.g., an imidazoline ring or a diphenol group) to generate novel lipophilic ethers such as bakuchiol-O-VE, phentolamine-O-VE, phenylethyl resorcinol-O-VE, 2-propanol-O-VE, and resveratrol-O-VE. Seven recombinant CYP enzymes were successfully expressed and purified in Escherichia coli. Integration of the results of recombinant human CYP incubation and molecular docking identified the central role of CYP3A4 in the cross-coupling metabolic pathway. Structural analysis revealed the π-π interactions, hydrogen bonds, and hydrophobic interactions between reactive xenobiotics and VE in the malleable active sites of CYP3A4. The consistency between the molecular docking results and the in vitro human cytochrome P450 evaluation shows that docking calculations can be used to screen molecules participating in cross-coupling metabolism. The results of this study provide supporting evidence for the overlooked toxicological effects induced by direct reactions between xenobiotics and endogenous metabolites during metabolic processes.

Revealing the Inner Changes of Component Composition Derived from DOM PARAFAC Based on Two-Dimensional Correlation Spectroscopy.

Plenty of humic acid components compositions are contained in dissolved organic matter (DOM) derived from composting. Fluorescence signals were employed to characterize the changes in DOM components in the component process. In the composting process, five individual DOM fluorescence parallel factor analysis (PARAFAC) components were identified. At the end of the composting, PARAFAC component C5, which represented high humification and complex structure compounds, was detected, but the simple structure DOM PARAFAC component C1 was absent. In this study, a technique combining EEM-PARAFAC with two-dimensional correlation spectroscopy (2DCOS) further supplied detailed information about the dynamics of DOM peaks in PARAFAC components. 2DCOS results showed that the variation of the peaks in PARAFAC components was different in the composting process. The formation of a complex DOM fluorescence substance was attributed to the residues from the simple fluorescence peak degradation. The evolution of the DOM fluorescence peaks in each PARAFAC component indicated that simple structure compounds helped the formation of the complex DOM fluorescence substance in the composting process. These results revealed that EEM/PARAFAC combined with 2DCOS could be used to track the evolution of DOM PARAFAC components during the composting process.

Insight into the Soil Dissolved Organic Matter Ligand-Phenanthrene-Binding Properties Based on Parallel Faction Analysis Combined with Two-Dimensional Correlation Spectroscopy.

Dissolved organic matter (DOM) can strongly bind to organic contaminants and control phenanthrene in soil. Herein, four individual parallel factor analysis (PARAFAC) components were found in soil DOM. Component C1 was the humic-like component ligand T, and component C2 was a combination of humic fluorophore ligands M1 and M2. Furthermore, components C3 and C4 were characterized as terrestrial and ubiquitous humic substances. Then, the modified Stern-Volmer complexation model was used to reveal soil DOM component-phenanthrene-binding properties. The overall binding characteristics of a PARAFAC component could not express the phenanthrene-binding properties. Therefore, two-dimensional correlation spectroscopy was used to reveal DOM ligand-phenanthrene-binding properties. After binding with phenanthrene, DOM ligands T, M2, A2, and C1 were quenched but DOM ligands M1, A1, and C2 were excited. The ligands with higher humification presented higher phenanthrene-binding ability. With these promising results, the DOM ligand-phenanthrene-binding characteristics offered theoretical support for soil pollution control.

Tetraphenylphosphonium Chloride-Enhanced Ionization Coupled to Orbitrap Mass Spectrometry for Sensitive and Non-targeted Screening of Polyhalogenated Alkyl Compounds from Limited Serum.

Although many types of halogenated compounds are known to bioaccumulate in humans, few are routinely biomonitored and many have remained uncharacterized in human exposome studies due to a lack of high-sensitivity and high-resolution analytical methods. In this study, we discovered tetraphenylphosphonium chloride (Ph4PCl, 10 µM) as a simple additive to the mobile phase, which enhanced the ionizations of polyhalogenated alkyl compounds (such as organochlorinated pesticides [OCPs], chlorinated paraffins [CPs], dechlorane plus [DPs], and some brominated flame retardants [BFRs]) in the form [M + Cl]- and boosted mass spectrometry responses by an average of 1-3 orders of magnitude at a resolution of 140,000. Ph4PCl-enhanced ionization coupled with a halogenation-guided screening process was used to establish a sensitive and non-targeted method that required only single-step sample preparation and identified Cl- and/or bromine-containing alkyl compounds. The method enabled the identification of ∼700 polyhalogenated compounds from 200 µL of human serum, 240 of which were known compounds: 33 short-chain CPs, 52 median-chain CPs, 97 long-chain CPs, 22 very short-chain CPs (vSCCPs), 19 OCPs, 13 DPs, and 4 BFRs. We also identified 325 emerging contaminants (34 unsaturated CPs, 285 chlorinated fatty acid methyl esters [CFAMEs], and 6 chloro-bromo alkenes) and 130 new contaminants (114 oxygen-containing CPs, 2 hexachlorocyclohexane structural analogs, and 11 amino-containing and 3 nitrate-containing chlorinated compounds). The full scan results highlighted the dominance of CPs, CFAMEs, vSCCPs, and dichlorodiphenyltrichloroethanes in the serum samples. Ph4PCl-enhanced ionization enabled the sensitive and non-targeted identifications of polyhalogenated compounds in small volumes of biological fluid.

Insight into complexation of Cd(II) and Cu(II) to fulvic acid based on feature recognition of PARAFAC combined with 2DCOS.

Fulvic acid which could govern the environmental geochemistry behavior of heavy metals is considered as the eco-friendly substances for controlling heavy metal pollutants in environment. Knowledge on the individual fulvic acid ligand is crucial to characterize the effect of fulvic acid on the migration and toxicity of metal pollutants. Herein, fulvic acid substances were analyzed by fluorescence quenching associated with parallel factor analysis (PARAFAC). Three components were identified based on PARAFAC. Furthermore, two-dimensional correlation spectroscopy (2DCOS) associated with complexation model were used to elucidate the Cd(II)- and Cu(II)-binding characteristics of the individual fulvic acid ligand. The Cd(II)- and Cu(II)-binding capability and speed of different fulvic acid ligands were revealed and theoretical guidance and technical support were provided for the practical application. The Cd(II) contaminated soil could be amended with high fulvic acid ligands A1 and Y2 containing composting products and the Cu(II) contaminated soil could be amended with high fulvic acid ligands Y1, T1 and A1 containing composting products to control the pollution and improve the soil condition. Based on these excellent results, the different fulvic acid ligands-contaminants-binding properties was characterized for the theoretical supporting of environmental pollution control.

Characteristics of oxytetracycline stress-sensitive microbe-dissolved organic matter component interactions during composting.

Dissolved organic matter (DOM) has important impacts on the transportation of antibiotics through chemical and biological processes in composting. The interaction between DOM and antibiotics is reciprocal. The interaction between DOM ligands and antibiotics could be characterized based on a technique combining parallel factor analysis (PARAFAC) and microbial community structure analysis. However, PARAFAC cannot reveal the dynamic changes in each DOM peak in one PARAFAC component under antibiotic stress. In this study, two-dimensional correlation spectroscopy (2DCOS) combined with PARAFAC and bacterial community diversity analyses were employed to reveal the effects of oxytetracycline (OTC) stress and the key microorganisms on the transformation of different fluorescent peaks from DOM PARAFAC components during chicken manure composting. The results showed that OTC inhibits the transformation between DOM PARAFAC components by inhibiting the core microbial activities involved in the transformation of DOM components. Protein-like components (C1 and C2) were more sensitive to OTC residue, and components with a high humification degree promoted the degradation of OTC. The interaction between special DOM PARAFAC components and certain bacteria affects the degradation of OTC. The DOM PARAFAC components A2(C1), B1(C2), B2(C2) and Z1(C4) enhanced OTC degradation by stimulating the genera Pseudomonas, Glycomyces and Hyphomicrobium. With these promising results, the true effect of DOM PARAFAC components on the degradation of OTC can be revealed, which is helpful for addressing antibiotic contamination to improve the bioavailability of compost products.

Enzyme-Mediated Reactions of Phenolic Pollutants and Endogenous Metabolites as an Overlooked Metabolic Disruption Pathway.

It is generally recognized that phenol-containing molecules mainly undergo phase II metabolic reactions, whereas glucuronide and sulfate are conjugated to form water-soluble products. Here, we report direct reactions of phenolic pollutants (triclosan, alkylphenol, bisphenol A [BPA], and its analogues) and some endogenous metabolites (vitamin E [VE] and estradiol) to generate new lipophilic ether products (e.g., BPA-O-VEs and alkylphenol-O-estradiol). A nontargeted screening strategy was used to identify the products in human liver microsome incubations, and the most abundant products (BPA-O-VEs) were confirmed via in vivo exposure in mice. BPA-O-VEs were frequently detected in sera from the general population at levels comparable to those of glucuronide/sulfate-conjugated BPA. Recombinant human cytochrome P450s were applied to find that CYP3A4 catalyzed the formation of these newly discovered ether metabolites by linking the VE hydroxyl group to the BPA phenolic ring, leading to the significantly reduced antioxidative activities of BPA-O-VEs compared to VEs. The effects of the reaction on the homeostasis of reacted biomolecules were finally assessed by in vitro assay and in vivo mice exposures. The generation of BPA-O-VEs decreased the VE concentrations and increased the reactive oxygen species generation after exposure to BPA at environmentally relevant concentrations. The identified reactions provided an overlooked metabolic disruption pathway for phenolic pollutants.

Characterization of mercury binding to different molecular weight fractions of dissolved organic matter.

Dissolved organic matter (DOM) can strongly complex with various contaminants. Therefore, DOM was deemed as an environmentally friendly substance for controlling the mobility, bioavailability, speciation, toxicity, and fate of metal contaminants in environment. In this study, composting-derived DOM was categorized into three fractions based on different molecular weights (MWs). Furthermore, parallel faction analysis (PARAFAC), two-dimensional correlation spectroscopy (2DCOS), and a complexation model were employed to reveal the contaminate-binding characterization. Two PARAFAC fluorescence components were identified in the MW < 1 kDa and the 1 kDa < MW < 5 kDa fractions, respectively. In the MW > 5 kDa fraction, three PARAFAC components were identified. Protein-like component C5 did not have the Hg2+-binding ability. Moreover, the results showed that not all the DOM ligands could bind with contaminants, but a high humification degree of composting DOM ligands could strongly bind Hg2+. In addition, DOM ligand with a low humification degree DOM ligands presented a higher Hg2+-binding speed. Subsequently, DOM from different MWs DOM could be applied separately to the different pollution forms. With these promising results, the different DOM ligand-Hg2+-binding properties were characterized to provide theoretical support for environmental pollution control.

Determination and occurrence of sulfonamide transformation products in surface waters.

The transformation products of sulfonamides (SAs) have raised increasing environmental and health concerns in recent years, but information on their analysis and environmental fates remains limited. In this study, an analytical method using liquid chromatography with tandem mass spectrometry (LC-MSMS) was optimized to simultaneously analyze 9 SA transformation products and 14 SAs in water samples. This method was applied to investigate the occurrence of antibiotics in three urban rivers in Beijing, and all of the target compounds were detected. N-acetylsulfamethoxazole, N-acetylsulfapyridine, and N-acetylsulfamethazine were found to be the predominant acetyl SAs in the aquatic environment, and high frequencies of hydroxylated SA (5-hydroxysulfapyridine) and glucuronide-conjugated SA (sulfamethoxazole ß-D-glucuronide) were also detected. The SA transformation products accounted for 22-32% of the total concentrations of SAs and their transformation products in the water samples. The pollution levels of the compounds exerted only minor effects on the proportions of the SA transformation products. The compound-specific transformation of sulfamethoxazole, sulfapyridine, and sulfadiazine in the water samples was consistent with their acetylation efficiencies in metabolic processes in organisms, which suggests that the SA-acetylated products were derived mainly from biological metabolism in humans or animals. This finding was supported by the fact that environmental degradation exerts a weak effect on SA profiles in the water samples.

Xenobiotics Targeting Cardiolipin Metabolism to Promote Thrombosis in Zebrafish.

Exposure to environmental pollutants is an important factor contributing to the development and severity of thrombosis. However, the important physiological molecules in the thrombotic processes affected by environmental exposures remain unknown. In this study, we show that exposure to environmental chemicals disrupts the equilibrium of cardiolipins (CLs), and directing CL synthesis promotes thrombosis. Using an untargeted metabolomics approach, approximately 3030 molecules were detected in zebrafish embryos exposed to 11 environmental chemicals and automatically clustered into a network. Interconnectivity among CLs and linoleates or isoxanthopterin was discovered through the highly consistent variations in the coregulated metabolites in the network. The chemical exposure resulted in significant upregulation of CLs through influencing the enzymatic activities of phospholipase A2, cardiolipin synthase, and lysocardiolipin acyltransferase. Consequently, metabolic disorders of CLs affected the levels of anticardiolipin antibodies, disrupted the homeostasis between platelet thromboxane A2 and endothelial prostacyclin, and promoted thrombotic events including heart ischemia and tachycardia. Our study thus reveals the common molecular mechanisms underlying the CL-induced thrombosis targeted by environmental exposures.

Oxytetracycline stress reconstruct the core microbial community related to nitrogen transformation during composting.

This study investigated oxytetracycline (OTC) effects on nitrogen (N) transformation and bacterial community diversity during chicken manure composting. The addition of OTC inhibited nitrifying bacteria, resulted in a decrease in the transformation of NH4+-N to NO3--N during composting, and affected in the order T3 (32.76%) > T2 (28.76%) > T1 (17.02%) > CK. The OTC could act as an inhibitor against core microbial growth, leading to a delay effect during composting. 16S rRNA sequencing was employed for the functional prediction, and results indicated the bacterial community related to N transformation reconstructed under OTC stress. The core microorganisms were changed after OTC addition, with the emergence of Bacillus and Thermobifida, which could inhibit the N transformation by network analysis. Therefore, core microorganisms could be regulated to reduce the negative of OTC impacts on N transformation and thus reduce N loss during composting.

Protein-affinity guided identification of chlorinated paraffin components as ubiquitous chemicals.

Chlorinated paraffins (CPs) have been extensively examined to identify their components. Short-chain CPs with a carbon number of 10-13 have been strictly restricted or banned due to their addition to the list of Persistent Organic Pollutants in the world. However, more constituents with potential toxicities in these complicated mixtures are still unclear. In the present study, a purification method based on the protein affinity of thyroid hormone-related proteins (transthyretin and thyroid receptor) was established. The protein-based affinity extraction coupled with high-throughput scanning successfully discover a new group of chlorinated compounds (CP(O2)) in commercial CP mixtures. The CP(O2)s were purified from the commercial mixtures and identified to be chlorinated fatty acid methyl esters (CFAMEs) with a carbon chain length of 17-19 and 3-11 chlorines by a combination of liquid-liquid extraction, hydrolysis, Fourier transform infrared spectrometry and Orbitrap mass spectrometry. The newly identified CFAMEs were found to be ubiquitous in the environmental matrices, and concentration ratios of ∑CFAMEs/∑CPs ranged from 0.01 to 35 in air, soil and food samples. CFAMEs were also detected in blood samples of general populations, and accumulated in humans through dietary uptake. CFAMEs can compete with T4 for binding TTR with higher potencies than CPs, possibly leading to disruptions of thyroid hormone homeostasis.

Revealing the Inner Dynamics of Fulvic Acid from Different Compost-Amended Soils through Microbial and Chemical Analyses.

The formation of fulvic acid (FA), an aromatic compound, is affected by the compost amendment. This study aimed to assess the extent of the humification of FA in soil amended with seven different composts. Results showed that composts improved the FA concentration in soil. Parallel factor (PARAFAC) analysis, combined with hetero-two-dimensional correlation spectroscopy (hetero-2DCOS), indicated that the inner changes in FA components determined the evolution of mineralization. The diversity in the composts used and the dominant microbes present might be responsible for the evolution of different mechanisms of FA transformation. Structural equation models (SEMs) demonstrated that the FA components were transformed directly by microbes, or indirectly via changes in the total organic carbon (TOC) and total nitrogen (TN) contents, C:N ratio, humic substance (HS) levels, and humic acid (HA): FA ratio, which regulate the microbial community structure. Our results will be useful for improving the bioavailability of compost products and realizing sustainable utilization of the soil.

Parallel faction analysis combined with two-dimensional correlation spectroscopy reveal the characteristics of mercury-composting-derived dissolved organic matter interactions.

Dissolved organic matter (DOM) is regarded as the environmentally friendly substance. Strong complexes could be formed between DOM and heavy metals. Thus, the distribution, bioavailability, toxicity, and fate of heavy metals could be controlled in the environment. The widely spread method for characterizing metal-organic interactions is restricted to combine parallel faction analysis (PARAFAC) with the complexation model. However, a DOM PARAFAC component always contains two or more peaks. Therefore, the traditional method cannot reveal the inner changes of PARAFAC components or whether all the DOM peaks in one PARAFAC component are bound with metal during the metal-organic binding process. In this work, two-dimensional correlation spectroscopy (2DCOS) combined with PARAFAC and the complexation model were employed to reveal the binding speed and ability of different fluorescent peaks from DOM PARAFAC components during the binding process of mercury (Hg2+) to DOM. The results in this study showed that during the Hg2+-DOM binding process, fluorescent peaks in tryptophan-like component all presented Hg2+-binding ability. However, only humic-like component ligands showed Hg2+-binding ability. With these promising results, the true Hg2+ binding rate and ability of different DOM ligands can be revealed, which is helpful for addressing environmental pollution.